High refractive-index, hydrophilic, arylsiloxy-containing macromonomers and polymers, and ophthalmic devices comprising such polymers

ABSTRACT

Hydrophilic, arylsiloxy-containing macromonomers have at least a terminal hydrophilic group attached to an arylsiloxy group. The aryl groups attached to siloxy groups can be substituted with other hydrophilic groups. Polymers comprising such hydrophilic, arylsiloxy-containing macromonomers avoid or reduce the risk of forming vacuoles of absorbed water. Furthermore, such polymers have high refractive index, and, thus, are advantageously used for making ophthalmic devices, such as intraocular lenses, contact lenses, corneal rings, corneal inlays, and keratoprostheses.

BACKGROUND OF THE INVENTION

The present invention relates to high refractive-index, hydrophilic,arylsiloxy-containing monomers, macromonomers, and polymers, andophthalmic devices comprising such polymers.

Since the 1940s ophthalmic devices in the form of intraocular lens(“IOL”) implants have been utilized as replacements for diseased ordamaged natural ocular lenses. In most cases, an intraocular lens isimplanted within an eye at the time of surgically removing the diseasedor damaged natural lens, such as for example, in the case of cataracts.For decades, the preferred material for fabricating such intraocularlens implants was poly(methyl methacrylate), which is a rigid, glassypolymer.

Softer, more flexible IOL implants have gained in popularity in morerecent years due to their ability to be compressed, folded, rolled orotherwise deformed. Such softer IOL implants may be deformed prior toinsertion thereof through an incision in the cornea of an eye. Followinginsertion of the IOL in an eye, the IOL returns to its originalpre-deformed shape due to the memory characteristics of the softmaterial. Softer, more flexible IOL implants as just described may beimplanted into an eye through an incision that is much smaller, i.e.,less than 4.0 mm, than that necessary for more rigid IOLs, i.e., 5.5 to7.0 mm. A larger incision is necessary for more rigid IOL implantsbecause the lens must be inserted through an incision in the corneaslightly larger than the diameter of the inflexible IOL optic portion.Accordingly, more rigid IOL implants have become less popular in themarket since larger incisions have been found to be associated with anincreased incidence of postoperative complications, such as inducedastigmatism.

With recent advances in small-incision cataract surgery, increasedemphasis has been placed on developing soft, foldable materials suitablefor use in artificial IOL implants. In general, the materials of currentcommercial IOLs fall into one of three general categories: silicones,hydrophilic acrylics and hydrophobic acrylics.

In general, high water content hydrophilic acrylics, or “hydrogels,”have relatively low refractive indices, making them less desirable thanother materials with respect to minimal incision size. Lowrefractive-index materials require a thicker IOL optic portion toachieve a given refractive power. Silicone materials may have a higherrefractive index than high-water content hydrogels, but some particularsilicone materials tend to unfold explosively after being placed in theeye in a folded position. Explosive unfolding can potentially damage thecorneal endothelium and/or rupture the natural lens capsule andassociated zonules. Low glass-transition-temperature hydrophobic acrylicmaterials are desirable because they typically have a high refractiveindex and unfold more slowly and more controllably than siliconematerials. Unfortunately, low glass-transition-temperature hydrophobicacrylic materials, which contain little or no water initially, tend toabsorb water over time and form pockets of water or vacuoles in vivo,causing light reflections or “glistenings.” Furthermore, it may bedifficult to achieve ideal folding and unfolding characteristics due tothe temperature sensitivity of some acrylic polymers.

Because of the noted shortcomings of current polymeric materialsavailable for use in the manufacture of ophthalmic implants, there is aneed for stable, biocompatible polymeric materials having desirablephysical characteristics and refractive indices.

SUMMARY OF THE INVENTION

In general, the present invention provides hydrophilic,siloxy-containing monomers and macromonomers having high refractiveindices and polymeric compositions comprising such monomers ormacromonomers.

In one aspect, a monomer or a macromonomer of the present invention hasat least an aryl group and at least a hydrophilic group attacheddirectly or indirectly to a silicon atom of a siloxy group, and at leasta polymerizable functional group.

In another aspect, a hydrophilic, arylsiloxy-containing monomer of thepresent invention has a formula of

wherein the R¹ groups are the same or different and are selected fromthe group consisting of unsubstituted and substituted C₆-C₂₄ aromaticgroups, saturated straight C₁-C₁₀ hydrocarbons, unsaturated straightC₁-C₁₀ hydrocarbons, saturated branched C₃-C₁₀ hydrocarbons, unsaturatedbranched C₃-C₁₀ hydrocarbons, saturated cyclic C₃-C₁₀ hydrocarbons,unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀ alkyloxysubstituents, and at least one R¹ group is selected from the groupconsisting of unsubstituted and substituted C₆-C₂₄ aromatic groups; R²are independently selected from the group consisting of hydrogen,saturated straight C₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀hydrocarbons, saturated branched C₃-C₁₀ hydrocarbons, unsaturatedbranched C₃-C₁₀ hydrocarbons, saturated cyclic C₃-C₁₀ hydrocarbons,unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀ alkyloxysubstituents; D and D′ are the same or different divalent groups; Q is adivalent group (such as divalent unsubstituted hydrocarbons orsubstituted hydrocarbons) or an alkyleneoxy or poly(alkyleneoxy) group;each E group is independently selected from the group consisting ofunsubstituted and substituted pyrrolidone, hydroxyethyl group,ethoxyethanol group, ethoxymethoxy group, glyceryl group, amides,carboxylic acid, sulfonic acid, phosphonic acid, and alcohols; each Ggroup is independently selected from the group consisting ofpolymerizable functional groups; n and m are independent integers; 1≦n,m≦3; and 4−n−m≧0.

In another aspect, the present invention provides a polymerizablehydrophilic, siloxy-containing macromonomer, wherein a plurality ofsilicon atoms has aromatic side groups.

In still another aspect, a polymerizable hydrophilic,arylsiloxy-containing macromonomer has a formula of

wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are independentlyselected from the group consisting of unsubstituted and substitutedC₆-C₂₄ aromatic groups, saturated straight C₁-C₁₀ hydrocarbons,unsaturated straight C₁-C₁₀ hydrocarbons, saturated branched C₃-C₁₀hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons, saturated cyclicC₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀ hydrocarbons, andC₁-C₁₀alkyloxy substituents; R^(3a), R^(3b), R^(4a), and R^(4b) areindependently selected from the group consisting of unsubstituted andsubstituted C₆-C₂₄ aromatic groups; D¹, D², D³, and D⁴ are independentlydivalent linking groups; Q is a divalent group, such as divalenthydrocarbon, substituted hydrocarbon, alkyleneoxy, or poly(alkyleneoxy)group; at least a plurality of E groups is independently selected fromthe group consisting of unsubstituted and substituted pyrrolidone,hydroxyethyl group, ethoxyethanol group, ethoxymethoxy group, glycerylgroup, amides, carboxylic acid, sulfonic acid, phosphonic acid, andalcohols; G and G′ are independently selected from the group consistingof polymerizable functional groups; t and w are integers; 2≦t≦500; and1≦w≦100. In one embodiment, some E groups can be hydrogen or alkylgroups (e.g., alkyl groups having 1-20 carbon atoms, inclusive).

In still another aspect, a polymeric composition comprises a homopolymerof a hydrophilic, arylsiloxy-containing monomer or macromonomer of thepresent invention, or a copolymer of at least two hydrophilic,arylsiloxy-containing monomers or macromonomers of the presentinvention, or a copolymer of a hydrophilic, arylsiloxy-containingmonomer or macromonomer of the present invention and at least one othermonomer or macromonomer.

In still another aspect, said at least one other monomer is selectedfrom hydrophilic monomers, hydrophobic monomers and macromonomers, andcombinations thereof.

In yet another aspect, the present invention provides a method of makinga high refractive index hydrophilic, arylsiloxy-containing monomer ormacromonomer. The method comprises reacting an arylsiloxy-containingmonomer or macromonomer with at least a hydrophilic monomer ormacromonomer, such that the resulting compound has a refractive indexgreater than about 1.4, preferably greater than 1.43.

In yet another aspect, the present invention provides a method of makinga hydrophilic polymeric composition having a high refractive index. Themethod comprises polymerizing a hydrophilic, arylsiloxy-containingmonomer or macromonomer, or polymerizing such a monomer or macromonomerand at least a different monomer or macromonomer, such that therefractive index is greater than about 1.4, preferably from about 1.4 toabout 1.6. In one embodiment, the refractive index is from about 1.45 toabout 1.58.

In yet another aspect, an ophthalmic device comprises a polymericmaterial that comprises units of at least a hydrophilic,arylsiloxy-containing monomer or macromonomer of the present invention.

Other features and advantages of the present invention will becomeapparent from the following detailed description and claims.

DETAILED DESCRIPTION OF THE INVENTION

In general, the present invention provides hydrophilic,siloxy-containing monomers and macromonomers having high refractiveindices and polymeric compositions comprising such monomers ormacromonomers. A monomer or a macromonomer of the present invention hasat least a polymerizable functional group, at least an aryl group, andat least a hydrophilic group, each attached directly or indirectly to asilicon atom of a siloxy group. A hydrophilic group can be attachedindirectly to a silicon atom through a linking group that can compriseother hydrophobic or hydrophilic groups or a combination thereof. Ahydrophilic group also can be attached through another siloxy group. Thepolymeric compositions of the present invention have refractive index ofabout 1.4 or greater. In some embodiments, the refractive index is inthe range from about 1.4 to about 1.7. In some other embodiments, therefractive index is in the range from about 1.45 to about 1.6.

In one aspect, a polymeric composition of the present invention has anequilibrium water content of greater than about 4.5 percent (by weight),thus avoiding problems related to the formation of water vacuoles. Inaddition, a polymeric composition of the present invention can have arelatively high elongation, such as about 80 percent or greater.Accordingly, in many aspects, the subject polymeric compositions aremore suitable for use in the manufacture of ophthalmic devices than manyprior-art polymeric materials.

Current commercial hydrophobic acrylic-based ophthalmic products havewater content less than 4.5 percent by weight. These hydrophobicproducts tend to absorb water over time in vivo and form water vacuolesor “glistenings.” In contrast, a polymeric composition comprising unitsof hydrophilic, arylsiloxy-containing monomers or macromonomers of thepresent invention tend to absorb water rapidly to equilibrium level.Although applicants do not wish to be bound to any particular theory, itis believed that the absorbed water also is distributed throughout thepolymeric composition because of its association with the hydrophilicsubstituents in the aromatic monomers. Therefore, polymeric compositionsof the present invention do not present the risk of formation of watervacuoles in vivo.

In one aspect, a hydrophilic, arylsiloxy-containing monomer of thepresent invention has a formula of

wherein the R¹ groups are the same or different and are selected fromthe group consisting of unsubstituted and substituted C₆-C₂₄ aromaticgroups, saturated straight C₁-C₁₀ hydrocarbons, unsaturated straightC₁-C₁₀ hydrocarbons, saturated branched C₃-C₁₀ hydrocarbons, unsaturatedbranched C₃-C₁₀ hydrocarbons, saturated cyclic C₃-C₁₀ hydrocarbons,unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀alkyloxy substituents,and at least one R¹ group is selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄aromatic groups substituted with at least a hydrophilic substituent); R²are independently selected from the group consisting of hydrogen,saturated straight C₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀hydrocarbons, saturated branched C₃-C₁₀ hydrocarbons, unsaturatedbranched C₃-C₁₀ hydrocarbons, saturated cyclic C₃-C₁₀ hydrocarbons,unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀ alkyloxysubstituents; D and D′ are the same or different divalent groups(including divalent unsubstituted hydrocarbons, substitutedhydrocarbons, alkoxy, arylene, alkyl silyl, or siloxy groups); Q is adivalent group (such as one selected from the group consisting ofdivalent unsubstituted hydrocarbon, substituted hydrocarbon,alkyleneoxy, or poly(alkyleneoxy) groups); each E group is independentlyselected from the group consisting of unsubstituted and substitutedpyrrolidone, hydroxyethyl group, ethoxyethanol group, ethoxymethoxygroup, glyceryl group, amides, carboxylic acid, sulfonic acid,phosphonic acid, and alcohols; each G group is independently selectedfrom the group consisting of polymerizable functional groups; n and mare independent integers; 1≦n, m≦3; and 4−n−m≧0. In one embodiment, twoR¹ groups attached to the same silicon atom can be the same, butdifferent from two R¹ groups attached to another silicon atom. Inanother embodiment, all R¹ groups are the same.

Non-limiting examples of aromatic groups are phenyl, biphenyl, cumenyl,mesityl, tolyl, xylyl, benzyl, benzhydryl, cinnamyl, phenethyl, styryl,trityl, naphthyl, anthryl, phenanthryl, chrysyl, and derivativesthereof. Preferably, R¹ is a C₆-C₂₄ aromatic group substituted with atleast a hydrophilic substituent.

In one embodiment, R¹ is a phenyl group; preferably, a phenyl grouphaving at least a hydrophilic substituent. Alternatively, R¹ is a phenylgroup having at least a hydrophilic group and another substitutent.

In another embodiment, R¹ is an aromatic other than phenyl; preferably,having at least a hydrophilic substituent.

In another embodiment, at least a hydrophilic substituent on thearomatic group is selected from the group consisting of carboxy, alcohol(including monohydric and polyhydric alcohols), and alkoxy substiuents,and combinations thereof.

In another embodiment, at least a hydrophilic substituent on thearomatic group is selected from the group consisting of —COOH,—(CH₂)₂—CH₂OH, —(CHOH)₂—CH₂OH, —CH₂—CHOH—CH₂OH, and combinationsthereof.

In still another embodiment, at least a hydrophilic substituent on thearomatic group is a poly(alkylene glycol), such as poly(ethylene glycol)having a formula of —(O—CH₂—CH₂)_(k)OH or —(O—CH₂—CH₂)_(k)—OCH₃, whereink is an integer and 1≦k≦100, preferably 1≦k≦50, and more preferably,1≦k≦20.

In a further embodiment, said hydrophilic substituent is selected fromthe group consisting of carboxamide, dialkyl-substituted carboxamide,amino, quaternary ammonium, alkanolamino, sulfonate, phosphonate,sulfate, phosphate, ureido, substituted sugars, and combinationsthereof.

In another embodiment, R¹ is selected from the group consisting ofhydrogen and saturated straight C₁-C₁₀ hydrocarbons.

In another aspect, G is a reactive functional group selected from thegroup consisting of vinyl, allyl, butadienyl, acryloyl, acryloyloxy,methacryloyl, methacryloyloxy, epoxy, itaconyl, maleimido, acrylamido,methacrylamido, fumaryl, styryl, and combinations thereof.

In another aspect, G is selected from the group consisting of vinyl,styryl, acryloyloxy, methacryloyloxy, acrylamido, and methacrylamido.

In another aspect, D and D′ are divalent groups independently selectedfrom the group consisting of saturated straight C₁-C₁₀ hydrocarbons,unsaturated straight C₁-C₁₀ hydrocarbons, saturated branched C₃-C₁₀hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons, saturated cyclicC₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀ hydrocarbons, andalkyloxy substituents. Preferably, D and D′ are saturated straightC₁-C₁₀ hydrocarbon divalent groups.

In one embodiment, D and D′ are the same divalent group of —(CH₂)_(x)—,wherein x is an integer in the range from 1 to, and including, 10; e.g.,methylene, ethylene, trimethylene, tetramethylene, or pentamethylene.

Q is an alkyleneoxy or a poly(alkyleneoxy) group. Non-limiting examplesof Q are ethyleneoxy, propyleneoxy, poly(ethyleneoxy),poly(propyleneoxy), and poly(ethyleneoxy-propyleneoxy). The number ofrepeating units of such a poly(alkyleneoxy) group can be in the rangefrom 2 to, and including, 100; preferably, from 2 to 50; and morepreferably, from 2 to 20.

In one embodiment, a hydrophilic, arylsiloxy-containing monomer of thepresent invention has a formula

wherein R is hydrogen or CH₃; Ph is unsubstituted or substituted phenylgroup; u, v, x, z, y¹, y², and y³ are independently selected integers;1≦u, v, x, z≦10; and 0≦y¹, y², y³≦100.

In one embodiment, u, v, x, and z are the same and are 1, 2, 3, or 4. Inanother embodiment, x and v are the same.

In another embodiment, 1≦y¹, y², y³≦50. Alternatively, 1≦y¹, y², y³≦20.

In still another embodiment, Ph is the phenyl group substituted with oneor more of the hydrophilic substituents disclosed above for aromaticgroups. Non-limiting examples of suitable substituted phenyl groups arerepresented by

wherein R⁵ is selected from the group consisting of —COOH, —CH₂CH₂OH,—CH₂CH₂OCH₂CH₂OR (where R is H or CH₃), —CH₂CH(OH)CH₂OH, —C(O)NH₂, and—C(O)N(CH₃)₂.

In another aspect, the present invention provides a polymerizablehydrophilic, arylsiloxy-containing macromonomer having a formula of

wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same or differentand are selected from the group consisting of unsubstituted andsubstituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄ aromatic groupssubstituted with at least a hydrophilic substituent), saturated straightC₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄aromatic groups substituted with at least a hydrophilic substituent);D¹, D², D³, and D⁴ are independently divalent linking groups; Q is adivalent group, such as divalent hydrocarbon, substituted hydrocarbon,alkyleneoxy, or poly(alkyleneoxy) groups; at least a plurality of Egroups is independently selected from the group consisting ofunsubstituted and substituted pyrrolidone, hydroxyethyl group,ethoxyethanol group, ethoxymethoxy group, glyceryl group, amides,carboxylic acid, sulfonic acid, phosphonic acid, and alcohols; G and G′are independently selected from the group consisting of polymerizablefunctional groups; t and w are integers; 2≦t≦500; and 1≦w≦100. In oneembodiment, 2≦t≦200. In another embodiment, ≦t≦100. In still anotherembodiment, 1≦w≦50. In still another embodiment, 1≦w≦20.

Non-limiting examples of aromatic side groups suitable for R¹, R^(2a),R^(2b), R^(2c), R^(2d), R^(3a), R^(3b), R^(4a), and R^(4b) are phenyl,biphenyl, cumenyl, mesityl, tolyl, xylyl, benzyl, benzhydryl, cinnamyl,phenethyl, styryl, trityl, naphthyl, anthryl, phenanthryl, chrysyl, andderivatives thereof. Preferably, such side groups are a C₆-C₂₄ aromaticgroup substituted with at least a hydrophilic substituent. In oneembodiment, two side groups attached to the same silicon atom can be thesame, but different from two side groups attached to another siliconatom. Alternatively, all side groups attached to silicon atoms can bethe same.

In one embodiment, R^(2a), R^(2b), R^(2c), R^(2d), R^(3a), R^(3b),R^(4a), and R^(4b) are the phenyl group; preferably, the phenyl grouphaving at least a hydrophilic substituent.

In another embodiment, R^(2a), R^(2b), R^(2c), R^(2d), R^(3a), R^(3b),R^(4a), and R^(4b) are aromatic groups other than phenyl; preferably,having at least a hydrophilic substituent.

In another embodiment, at least a hydrophilic substituent on thearomatic group is selected from the group consisting of carboxy, alcohol(including monohydric and polyhydric alcohols), alkoxy substiuents, andcombinations thereof.

In another embodiment, at least a hydrophilic substituent on thearomatic group is selected from the group consisting of —COOH,—CH₂CH₂OH, —(CH₂)₂—CH₂OH, —CH₂CH(OH)CH₂OH, —(CHOH)₂—CH₂OH, —C(O)NH₂,—C(O)N(CH₃)₂, and combinations thereof.

In still another embodiment, at least a hydrophilic substituent on thearomatic group is a poly(alkylene glycol), such as poly(ethylene glycol)having a formula of —(O—CH₂—CH₂)_(k)OH or —(O—CH₂CH₂)_(k)—OCH₃, whereink is an integer and 1≦k≦100, preferably 1≦k≦50, and more preferably,1≦k≦20.

In a further embodiment, said hydrophilic substituent is selected fromthe group consisting of carboxamide, dialkyl-substituted carboxamide,amino, alkanolamino, sulfonate, phosphonate, sulfate, phosphate, ureido,substituted sugars, and combinations thereof.

In another aspect, G and G′ are reactive functional groups selected fromthe group consisting of vinyl, allyl, butadienyl, acryloyl, acryloyloxy,methacryloyl, methacryloyloxy, epoxy, itaconyl, maleimido, acrylamido,methacrylamido, fumaryl, styryl, and combinations thereof.

In another aspect, G and G′ are selected from the group consisting ofvinyl, styryl, acryloyloxy, and methacryloyloxy.

In another aspect, D¹, D², D³, and D⁴ are divalent groups independentlyselected from the group consisting of saturated straight C₁-C₁₀hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and alkyloxy substituents. Preferably, D¹, D², D³, and D⁴are independently selected from the group consisting of saturatedstraight C₁-C₁₀ hydrocarbon divalent groups.

In one embodiment, D¹, D², D³, and D⁴ are the same divalent group of—(CH₂)_(x)—, wherein x is an integer in the range from 1 to, andincluding, 10; e.g., methylene, ethylene, trimethylene, tetramethylene,or pentamethylene.

Q is an alkyleneoxy or a poly(alkyleneoxy) group. Non-limiting examplesof Q are ethyleneoxy, propyleneoxy, poly(ethyleneoxy),poly(propyleneoxy), and poly(ethyleneoxy-propyleneoxy). The number ofrepeating units of such a poly(alkyleneoxy) group can be in the rangefrom 2 to, and including, 100; preferably, from 2 to 50; and morepreferably, from 2 to 20.

Hydrophilic, arylsiloxy-containing monomers and macromonomers of thepresent invention can be used to produce homopolymers or copolymershaving high refractive indices, such as for example about 1.4 orgreater. In some embodiments, the homopolymers or copolymers haverefractive indices in the range from about 1.4 to about 1.7; in someother embodiments, from about 1.45 to about 1.6.

Alternatively, a hydrophilic, arylsiloxy-containing monomer ormacromonomer of the present invention can be copolymerized with anotherhydrophilic or hydrophobic monomer to provide a polymer having highrefractive index, such as about 1.4 or greater.

Non-limiting examples of other hydrophilic monomers useful forpolymerization with one or more hydrophilic, arylsiloxy-containingmonomers or macromonomers of the present invention includeN,N′-dimethylacrylamide, glycerol methacrylate, N-vinylpyrrolidone, and2-hydroxyethyl methacrylate. Preferably, N,N′-dimethylacrylamide is usedfor increased hydrophilicity.

Non-limiting examples of other hydrophobic monomers useful forpolymerization with one or more hydrophilic, arylsiloxy-containingmonomers of the present invention include C₁-C₁₀ alkyl methacrylates(e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate,butyl methacrylate, octyl methacrylate, or 2-ethylhexyl methacrylate;preferably, methyl methacrylate to control mechanical properties),C₁-C₁₀ alkyl acrylates (e.g., methyl acrylate, ethyl acrylate, propylacrylate, or hexyl acrylate; preferably, butyl acrylate to controlmechanical properties), C₆-C₄₀ arylalkyl acrylates (e.g., 2-phenylethylacrylate, benzyl acrylate, 3-phenylpropyl acrylate, 4-phenylbutylacrylate, 5-phenylpentyl acrylate, 8-phenyloctyl acrylate, or2-phenylethoxy acrylate; preferably, 2-phenylethyl acrylate to increaserefractive index), and C₆-C₄₀ arylalkyl methacrylates (e.g.,2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutylmethacrylate, 5-phenylpentyl methacrylate, 8-phenyloctyl methacrylate,2-phenoxyethyl methacrylate, 3,3-diphenylpropyl methacrylate,2-(1-naphthylethyl) methacrylate, benzyl methacrylate, or2-(2-naphthylethyl) methacrylate; preferably, 2-phenylethyl methacrylateto increase refractive index). Other suitable hydrophobic monomersinclude silicon-containing monomers, especially aromatic-basedsilicon-containing monomer, such as3-methacryloyloxypropyldiphenylmethylsilane.

An embodiment of the hydrophilic, arylsiloxy-containing monomer havingFormula (III) can be produced by a method illustrated in Scheme 1. Inthe following reaction schemes, Ph represents an unsubstituted orsubstituted phenyl group.

Another embodiment of the hydrophilic, arylsiloxy-containing monomer ofthe present invention can be produced by a method illustrated in Scheme2.

Another embodiment of the hydrophilic, arylsiloxy-containing monomer ofthe present invention can be produced by a method illustrated in Scheme3.

In one aspect, a method for producing a polymerizable, hydrophilic,arylsiloxy-containing monomer of the present invention comprises: (a)providing an arylsiloxy-containing compound having the polymerizablegroup and at least a hydrosilyl group, and a hydrophilic compound havinga hydrophilic group and a functional group that is capable of reactingwith the hydrosilyl group; and (b) reacting the arylsiloxy-containingcompound and the hydrophilic compound under conditions and for a timesufficient to produce the polymerizable, hydrophilic,arylsiloxy-containing monomer.

An embodiment of hydrophilic, arylsiloxy-containing macromonomers of thepresent invention, as represented by Formula (IV), can be produced by amethod illustrated in Scheme 4. In Formula (IV), Ph is an unsubstitutedor substituted phenyl group; and p, q, r, s, and w are integers greaterthan or equal to 1; and t is an integer greater than 1.

In one aspect, a method for producing a hydrophilic,arylsiloxy-containing macromonomer of the present invention comprises:(a) providing an arylsiloxy-containing macromonomer having a pluralityof hydrosilyl groups, and at least a hydrophilic compound having ahydrophilic group and a functional group that is capable of reactingwith the hydrosilyl groups; and (b) reacting the arylsiloxy-containingmacromonomer and the hydrophilic compound under conditions and for atime sufficient to produce the hydrophilic, arylsiloxy-containingmacromonomer.

Homopolymers of a hydrophilic, arylsiloxy-containing monomer ormacromonomer of the present invention and copolymers comprising one ormore hydrophilic, arylsiloxy-containing monomers or macromonomers of thepresent invention and at least another monomer can be produced by freeradical polymerization. For example, the polymerization of thehydrophilic, arylsiloxy-containing monomer having Formula (III) and2-phenylethyl methacrylate (or 2-phenylethyl acrylate) can be carriedout in the presence of a thermal polymerization initiator (such as oneselected from the list of thermal polymerization initiators disclosedbelow) at a temperature in the range from about 20° C. to about 120° C.Alternatively, the polymerization can be carried out in the presence ofa photoinitiator selected from the list of photoinitiators disclosedbelow at a temperature in the range from about 20° C. to about 60° C. Adesired molar ratio of the monomers can be chosen and a desiredmolecular weight can be achieved by a skilled artisan. For example, thenumber of repeating units of each type of monomer can be in the rangefrom about 1 to about 100,000, or from 1 to about 50,000, or from 1 toabout 20,000, or from 1 to about 5,000.

Another exemplary hydrophilic copolymer comprises the monomer havingFormula (III); N,N′-dimethylacrylamide; and 2-phenylethyl methacrylate(or 2-phenylethyl acrylate). The polymerization reaction can be carriedout in the presence of a thermal polymerization initiator (such as oneselected from the list of thermal polymerization initiators disclosedbelow) at a temperature in the range from about 20° C. to about 120° C.Alternatively, the reaction can be carried out in the presence of aphotoinitiator selected from the list of photoinitiators disclosed belowat a temperature in the range from about 20° C. to about 60° C. Adesired molar ratio of the monomers can be chosen and a desiredmolecular weight can be achieved by a skilled artisan. For example, thenumber of repeating units of each of the monomers can be in the rangefrom about 1 to about 100,000, or from 1 to about 50,000, or from 1 to20,000.

A formulation for the production of a polymer comprising a hydrophilic,arylsiloxy-containing monomer or macromonomer of the present inventioncan include one or more crosslinking agents in an amount less than about10 percent by weight of the weight of all monomers and crosslinkingagents, if desired. In one embodiment, the crosslinking agents arepresent in an amount less than about 5 percent by weight. In anotherembodiment, the crosslinking agents are present in an amount less thanabout 2 percent by weight.

Non-limiting examples of suitable crosslinking agents include ethyleneglycol dimethacrylate (“EGDMA”); diethylene glycol dimethacrylate;ethylene glycol diacrylate; triethylene glycol dimethacrylate;triethylene diacrylate; allyl methacrylates; allyl acrylates;1,3-propanediol dimethacrylate; 1,3-propanediol diacrylate;1,6-hexanediol dimethacrylate; 1,6-hexanediol diacrylate; 1,4-butanedioldimethacrylate; 1,4-butanediol diacrylate; trimethylolpropanetrimethacrylate (“TMPTMA”); glycerol trimethacrylate; poly(ethyleneoxidemono- and di-acrylate); N,N′-dihydroxyethylene bisacrylamide; diallylphthalate; triallyl cyanurate; divinylbenzene; ethylene glycol divinylether; N,N′-methylene-bis-(meth)acrylamide; divinylbenzene;divinylsulfone; and the like.

Although not required, homopolymers or copolymers within the scope ofthe present invention may optionally have one or more strengtheningagents added prior to polymerization, preferably in quantities of lessthan about 80 weight percent but more typically from about 20 to about60 weight percent. Non-limiting examples of suitable strengtheningagents are described in U.S. Pat. Nos. 4,327,203; 4,355,147; and5,270,418; each of which is incorporated herein in its entirety byreference. Specific examples, not intended to be limiting, of suchstrengthening agents include cycloalkyl acrylates and methacrylates;e.g., tert-butylcyclohexyl methacrylate and isopropylcyclopentylacrylate.

One or more ultraviolet (“UV”) light absorbers may optionally be addedto the copolymers prior to polymerization in quantities less than about5 percent by weight. Suitable UV light absorbers for use in the presentinvention include for example, but are not limited to,β-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate;4-(2-acryloxyethoxy)-2-hydroxybenzophenone;4-methacryloyloxy-2-hydroxybenzophenone;2-(2′-methacryloyloxy-5′-methylphenyl)benzotriazole;2-(2′-hydroxy-5′-methacryloyloxyethyl phenyl)-2H-benzotriazole;2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole;2-(3′-tert-butyl-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole;2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole;2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole,and2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole.Preferably, the UV light absorber also has a polymerizable functionalgroup. In one embodiment, the preferred UV light absorbers areβ-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate and2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazole.

One or more suitable free radical polymerization initiators may bedesirably added to the copolymers of the present invention. Theseinitiators include thermal polymerization initiators andphotopolymerization initiators. Thermal polymerization initiatorsinclude organic peroxy compounds and azobis(organonitrile) compounds.Non-limiting examples of suitable organic peroxy compounds includeperoxymonocarbonate esters, such as tert-butylperoxy isopropylcarbonate; peroxydicarbonate esters, such asdi(2-ethylhexyl)peroxydicarbonate, di(sec-butyl)peroxydicarbonate, anddiisopropyl peroxydicarbonate; diacyl peroxides, such as2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide,lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide,p-chlorobenzoyl peroxide; peroxyesters, such as ter-butylperoxypivalate, tert-butylperoxy octylate, and tert-butylperoxy isobutyrate;methylethylketone peroxide; and acetylcyclohexane sulfonyl peroxide.Non-limiting examples of suitable azobis(organonitrile) compoundsinclude azobis(isobutyronitrile); 2,2′-azobis(2,4-dimethylpentanenitrile); 1,1′-azobiscyclohexanecarbonitrile; andazobis(2,4-dimethylvaleronitrile); and mixtures thereof. Preferably,such an initiator is employed in a concentration of approximately 0.01to 1 percent by weight of the total monomer mixture.

Representative UV photopolymerization initiators include those known inthe field, such as the classes of benzophenone and its derivatives,benzoin ethers, and phosphine oxides. Some non-limiting examples ofthese initiators are benzophenone; 4,4′-bis(dimethylamino)benzophenone;4,4′-dihydroxybenzophenone; 2,2-diethoxyacetophenone;2,2-dimethoxy-2-phenylacetophenone; 4-(dimethylamino)benzophenone;2,5-dimethylbenzophenone; 3,4-dimethybenzophenone;4′-ethoxyacetophenone; 3′-hydroxyacetophenone; 4′-hydroxyacetophenone;3-hydroxybenzophenone; 4-hydroxybenzophenone; 1-hydroxycyclohexyl phenylketone; 2-hydroxy-2-methylpropiophenone; 2-methylbenzophenone;3-methylbenzophenone; 4′-phenoxyacetophenone;2-methyl-4′-(methylthio)-2-morpholinopropiophenone; benzoin methylether; benzoin ethyl ether; diphenyl(2,4,6-trimethylbenzoyl)phosphineoxide. These initiators are commercially available from Sigma-Aldrich.Other photo polymerization initiators are known under the trade namesDarocur™ and Irgacure™, such as Darocur™ 1173(2-hydroxy-2-methyl-1-phenyl-1-propanone), Irgacure™ 651(2,2-dimethoxy-2-phenylacetophenone), Irgacure™ 819(phenyl-bis(2,4,6-trimethyl benzoyl)phosphine oxide), and Irgacure™ 184(1-hydroxy cyclohexyl phenyl ketone) from Ciba-Geigy, Basel,Switzerland.

The polymeric compositions of the present invention are transparent,flexible, of relatively high refractive index and of relatively highelongation. The polymeric compositions of the present invention with thedesirable physical properties noted above are particularly useful in themanufacture of ophthalmic devices such as, but not limited to,relatively thin, foldable IOLs, contact lenses, corneal rings, cornealinlays, and keratoprostheses. Furthermore, absorbed water in thepolymeric compositions of the present invention does not tend to formwater vacuoles. Thus, the polymeric compositions of the presentinvention are more advantageously used in ophthalmic device applicationsthan prior-art acrylic compositions.

IOLs having relatively thin optic portions are critical in enabling asurgeon to minimize surgical incision size. Keeping the surgicalincision size to a minimum reduces intraoperative trauma andpostoperative complications. A relatively thin IOL optic portion is alsocritical for accommodating certain anatomical locations in the eye suchas the anterior chamber and the ciliary sulcus. IOLs may be placed inthe anterior chamber for increasing visual acuity in either aphakic orphakic eyes, or placed in the ciliary sulcus for increasing visualacuity in phakic eyes.

The polymeric compositions of the present invention have the flexibilityrequired to allow implants manufactured from the same to be folded ordeformed for insertion into an eye through the smallest possiblesurgical incision, i.e., 3.5 mm or smaller.

In general, a method of making an ophthalmic device comprises: (a)providing a polymerizable composition comprising a hydrophilic,arylsiloxy-containing monomer or macromonomer of the present invention;and (b) curing the polymerizable composition under conditions and for atime sufficient to produce the ophthalmic device. The curing can becarried out such that the polymerizable composition is solidified intothe final form of the ophthalmic device or such that a solid article isfirst produced and the ophthalmic device is further shaped therefrom.

In one embodiment, the method of making an ophthalmic device comprises:(a) providing a polymerizable composition comprising a hydrophilic,arylsiloxy-containing monomer or macromonomer; (b) disposing thepolymerizable composition in a mold cavity, which forms a shape of theophthalmic device; and (c) curing the polymerizable composition under acondition and for a time sufficient to form the ophthalmic device;wherein the hydrophilic, arylsiloxy-containing monomer has a formula of

wherein the R¹ groups are the same or different and are selected fromthe group consisting of unsubstituted and substituted C₆-C₂₄ aromaticgroups, saturated straight C₁-C₁₀ hydrocarbons, unsaturated straightC₁-C₁₀ hydrocarbons, saturated branched C₃-C₁₀ hydrocarbons, unsaturatedbranched C₃-C₁₀ hydrocarbons, saturated cyclic C₃-C₁₀ hydrocarbons,unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀alkyloxy substituents,and at least one R¹ group is selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄aromatic groups substituted with at least a hydrophilic substituent); R²are independently selected from the group consisting of hydrogen,saturated straight C₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀hydrocarbons, saturated branched C₃-C₁₀ hydrocarbons, unsaturatedbranched C₃-C₁₀ hydrocarbons, saturated cyclic C₃-C₁₀ hydrocarbons,unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀ alkyloxysubstituents; D and D′ are the same or different divalent groups; Q is adivalent group (such as a divalent unsubstituted hydrocarbon,substituted hydrocarbon, alkyleneoxy, or poly(alkyleneoxy) group); eachE group is independently selected from the group consisting ofunsubstituted and substituted pyrrolidone, hydroxyethyl group,ethoxyethanol group, ethoxymethoxy group, glyceryl group, amides,carboxylic acid, sulfonic acid, phosphonic acid, and alcohols; each Ggroup is independently selected from the group consisting ofpolymerizable functional groups; n and m are independent integers; 1≦n,m≦3; and 4−n−m≧0; and wherein the hydrophilic, arylsiloxy-containingmacromonomer has a formula of

wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same or differentand are selected from the group consisting of unsubstituted andsubstituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄ aromatic groupssubstituted with at least a hydrophilic substituent), saturated straightC₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄aromatic groups substituted with at least a hydrophilic substituent);D¹, D², D³, and D⁴ are independently divalent linking groups; Q is adivalent group, such as divalent hydrocarbon, substituted hydrocarbon,alkyleneoxy, or poly(alkyleneoxy) group; at least a plurality of Egroups is independently selected from the group consisting ofunsubstituted and substituted pyrrolidone, hydroxyethyl group,ethoxyethanol group, ethoxymethoxy group, glyceryl group, amides,carboxylic acid, sulfonic acid, phosphonic acid, and alcohols; G and G′are independently selected from the group consisting of polymerizablefunctional groups; t and w are integers; 2≦t≦500; and 1≦w≦100. In oneembodiment, 2≦t≦200. In another embodiment, ≦t≦100. In still anotherembodiment, 1≦w≦50. In still another embodiment, 1≦w≦20.

In one embodiment of the method, at least a hydrophilic substituent onthe aromatic group is selected from the group consisting of carboxy,carboxamide, alcohol (including monohydric and polyhydric alcohols)substituents, and combinations thereof.

In another embodiment of the method, at least a hydrophilic substituenton the aromatic group is selected from the group consisting of —COOH,—(CH₂)₂—CH₂OH, —(CHOH)₂—CH₂OH, —CH₂—CHOH—CH₂OH, and combinationsthereof.

In still another embodiment, at least a hydrophilic substituent on thearomatic group is a poly(alkylene glycol), such as poly(ethylene glycol)having a formula of —(O—CH₂—CH₂)_(k)OH or —(O—CH₂—CH₂)_(k)—OCH₃, whereink is an integer and 1≦k≦100, preferably 1≦k≦50, and more preferably,1≦k≦20.

In a further embodiment, said hydrophilic substituent is selected fromthe group consisting of carboxamide, dialkyl-substituted carboxamide,amino, quaternary ammonium, alkanolamino, sulfonate, phosphonate,sulfate, phosphate, ureido, substituted sugars, and combinationsthereof.

In yet another embodiment, the polymerizable composition also comprisesa crosslinking agent, or a polymerization initiator, or both. Thepolymerization initiator is preferably a thermal polymerizationinitiator. The curing can be carried out at an elevated temperature suchas in the range from about ambient temperature to about 120° C. In someembodiments, the curing is carried out at a temperature from slightlyhigher than ambient temperature to about 100° C. A time from about 1minute to about 48 hours is typically adequate for the curing.

In another embodiment, the method of making an ophthalmic devicecomprises: (a) providing polymerizable composition comprising ahydrophilic, arylsiloxy-containing monomer or a macromonomer; (b)casting the polymerizable composition under a condition and for a timesufficient to form a solid block; and (c) shaping the block into theophthalmic device; wherein the hydrophilic, arylsiloxy-containingmonomer has a formula of

wherein the R¹ groups are the same or different and are selected fromthe group consisting of unsubstituted and substituted C₆-C₂₄ aromaticgroups, saturated straight C₁-C₁₀ hydrocarbons, unsaturated straightC₁-C₁₀ hydrocarbons, saturated branched C₃-C₁₀ hydrocarbons, unsaturatedbranched C₃-C₁₀ hydrocarbons, saturated cyclic C₃-C₁₀ hydrocarbons,unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀ alkyloxysubstituents, and at least one R¹ group is selected from the groupconsisting of unsubstituted and substituted C₆-C₂₄ aromatic groups(preferably, C₆-C₂₄ aromatic groups substituted with at least ahydrophilic substituent); R² are independently selected from the groupconsisting of hydrogen, saturated straight C₁-C₁₀ hydrocarbons,unsaturated straight C₁-C₁₀ hydrocarbons, saturated branched C₃-C₁₀hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons, saturated cyclicC₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀ hydrocarbons, and C₁-C₁₀alkyloxy substituents; D and D′ are the same or different divalentgroup; Q is a divalent group (such as divalent unsubstitutedhydrocarbon, substituted hydrocarbon, alkyleneoxy, or poly(alkyleneoxy)group); each E group is independently selected from the group consistingof unsubstituted and substituted pyrrolidone, hydroxyethyl group,ethoxyethanol group, ethoxymethoxy group, glyceryl group, amides,carboxylic acid, sulfonic acid, phosphonic acid, and alcohols; each Ggroup is independently selected from the group consisting ofpolymerizable functional groups; n and m are independent integers; 1≦n,m≦3; and 4−n−m≧0; and wherein the macromonomer has a formula of

wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same or differentand are selected from the group consisting of unsubstituted andsubstituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄ aromatic groupssubstituted with at least a hydrophilic substituent), saturated straightC₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups (preferably, C₆-C₂₄aromatic groups substituted with at least a hydrophilic substituent);D¹, D², D³, and D⁴ are independently divalent linking groups; Q is adivalent group, such as divalent hydrocarbon, substituted hydrocarbon,alkyleneoxy, or poly(alkyleneoxy) group; at least a plurality of Egroups is independently selected from the group consisting ofunsubstituted and substituted pyrrolidone, hydroxyethyl group,ethoxyethanol group, ethoxymethoxy group, glyceryl group, amides,carboxylic acid, sulfonic acid, phosphonic acid, and alcohols; G and G′are independently selected from the group consisting of polymerizablefunctional groups; t and w are integers; 2≦t≦500; and 1≦w≦100. In oneembodiment, 2≦t≦200. In another embodiment, ≦t≦100. In still anotherembodiment, 1≦w≦50. In still another embodiment, 1≦w≦20.

In one embodiment, said at least a hydrophilic substituent is selectedfrom the group consisting of carboxy, alcohols (including monohydric andpolyhydric alcohols), and combinations thereof.

In another embodiment, at least a hydrophilic substituent on thearomatic group is selected from the group consisting of —COOH,—(CH₂)₂—CH₂OH, —(CHOH)₂—CH₂OH, —CH₂—CHOH—CH₂OH, and combinationsthereof.

In still another embodiment, at least a hydrophilic substituent on thearomatic group is a poly(alkylene glycol), such as poly(ethylene glycol)having a formula of —(O—CH₂—CH₂)_(k)OH or —(O—CH₂—CH₂)_(k)—OCH₃, whereink is an integer and 1≦k≦100, preferably 1≦k≦50, and more preferably,1≦k≦20.

In a further embodiment, said hydrophilic substituent is selected fromthe group consisting of carboxamide, dialkyl-substituted carboxamide,amino, alkanolamino, sulfonate, phosphonate, sulfate, phosphate, ureido,substituted sugars, and combinations thereof.

In yet another embodiment, the polymerizable composition also comprisesa crosslinking agent, or a polymerization initiator, or both. Thepolymerization initiator is preferably a thermal polymerizationinitiator. The casting can be carried out at an elevated temperaturesuch as in the range from about 20° C. to about 120° C. In someembodiments, the casting is carried out at a temperature from slightlyhigher than ambient temperature to about 100° C. A time from about 1minute to about 48 hours is typically adequate for the polymerization.The shaping can comprise cutting the solid block into wafers, andlathing or machining the wafers into the shape of the final ophthalmicdevice.

Ophthalmic medical devices manufactured using polymeric compositions ofthe present invention are used as customary in the field ofophthalmology. For example, in a surgical cataract procedure, anincision is placed in the cornea of an eye. Through the corneal incisionthe cataractous natural lens of the eye is removed (aphakic application)and an IOL is inserted into the anterior chamber, posterior chamber orlens capsule of the eye prior to closing the incision. However, thesubject ophthalmic devices may likewise be used in accordance with othersurgical procedures known to those skilled in the field ofophthalmology.

While specific embodiments of the present invention have been describedin the foregoing, it will be appreciated by those skilled in the artthat many equivalents, modifications, substitutions, and variations maybe made thereto without departing from the spirit and scope of theinvention as defined in the appended claims.

1. A macromonomer having the formula

wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same or differentand are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups, saturated straightC₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups; D¹, D², D³, and D⁴are independently selected divalent linking groups; Q is a divalentgroup selected from the group consisting of divalent unsusbstitutedhydrocarbon groups, substituted hydrocarbon groups, alkyleneoxy groups,and poly(alkyleneoxy) groups; at least a plurality of E groups isindependently selected from the group consisting of unsubstituted andsubstituted pyrrolidone, hydroxyethyl group, ethoxyethanol group,ethoxymethoxy group, glyceryl group, amides, carboxylic acid, sulfonicacid, phosphonic acid, and alcohols; G and G′ are independently selectedfrom the group consisting of polymerizable functional groups; t and ware integers; 2≦t≦500; and 0≦w≦100.
 2. The macromonomer of claim 1,wherein each of R¹, R^(2a), R^(2b), R^(2c), R^(2d), R^(3a), R^(3b),R^(4a), and R^(4b) is independently selected from the group consistingof phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, benzyl, benzhydryl,cinnamyl, phenethyl, styryl, trityl, naphthyl, anthryl, phenanthryl,chrysyl, and derivatives thereof.
 3. The macromonomer of claim 2,wherein R^(2a), R^(2b), R^(2c), R^(2d), R^(3a), R^(3b), R^(4a), andR^(4b) are C₆-C₂₄ aromatic groups having at least a hydrophilicsubstituent.
 4. The macromonomer of claim 3, wherein said at least ahydrophilic substituent is selected from the group consisting ofcarboxy, monohydric alcohol, polyhydric alcohol, alkoxy substituents,and combinations thereof.
 5. The macromonomer of claim 3, whereinR^(2a), R^(2b), R^(2c), R^(2d), R^(3a), R^(3b), R^(4a), and R^(4b) havea formula of

wherein R⁵ is selected from the group consisting of —COOH, —CH₂CH₂OH,—(CH₂)₂—CH₂OH, —CH₂CH(OH)CH₂OH, —(CHOH)₂—CH₂OH, —C(O)NH₂, and—C(O)N(CH₃)₂.
 6. The macromonomer of claim 1, wherein G and G′ areselected from the group consisting of vinyl, allyl, butadienyl,acryloyl, acryloyloxy, methacryloyl, methacryloyloxy, epoxy, itaconyl,maleimido, acrylamido, methacrylamido, fumaryl, styryl, and combinationsthereof.
 7. The macromonomer of claim 1, wherein G and G′ are selectedfrom the group consisting of vinyl, acryloyloxy, methacryloyloxy, andstyryl.
 8. The macromonomer of claim 1, wherein each of D¹, D², D³, andD⁴ is selected from the group consisting of saturated straight C₁-C₁₀hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and alkyloxy substituents.
 9. The macromonomer of claim 1,wherein Q is selected from the group consisting of alkyleneoxy andpoly(alkyleneoxy).
 10. The macromonomer of claim 1, wherein Q isselected from the group consisting of ethyleneoxy, propyleneoxy,poly(ethyleneoxy), poly(propyleneoxy), andpoly(ethyleneoxy-propyleneoxy), and wherein a number of repeating unitsof each of said poly(ethyleneoxy), poly(propyleneoxy), andpoly(ethyleneoxy-propyleneoxy) groups is in a range from 2 to about 100.11. A polymeric comprising units derived from a hydrophilic,arylsiloxy-containing macromonomer having a formula of

wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same or differentand are selected from the group consisting of unsubstituted andsubstituted C₆-C₂₄ aromatic groups, saturated straight C₁-C₁₀hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups; D¹, D², D³, and D⁴are independently divalent linking groups; Q is a divalent groupselected from the group consisting of divalent unsusbstitutedhydrocarbon groups, substituted hydrocarbon groups, alkyleneoxy groups,and poly(alkyleneoxy) groups; at least a plurality of E groups isindependently selected from the group consisting of unsubstituted andsubstituted pyrrolidone, hydroxyethyl group, ethoxyethanol group,ethoxymethoxy group, glyceryl group, amides, carboxylic acid, sulfonicacid, phosphonic acid, and alcohols; G and G′ are independently selectedfrom the group consisting of polymerizable functional groups; t and ware integers; 2≦t≦500; and 0≦w≦100.
 12. The polymeric composition ofclaim 11, wherein each of R¹, R^(2a), R^(2b), R^(2c), R^(2d), R^(3a),R^(3b), R^(4a), and R^(4b) is independently selected from the groupconsisting of phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, benzyl,benzhydryl, cinnamyl, phenethyl, styryl, trityl, naphthyl, anthryl,phenanthryl, chrysyl, and derivatives thereof.
 13. The polymericcomposition of claim 11, wherein R^(2a), R^(2b), R^(2c), R^(2d), R^(3a),R^(3b), R^(4a), and R^(4b) are selected from the group consisting ofunsubstituted C₆-C₂₄ aromatic groups and C₆-C₂₄ aromatic groups havingat least a hydrophilic substituent.
 14. The polymeric composition ofclaim 13, wherein said at least a hydrophilic substituent is selectedfrom the group consisting of carboxy, monohydric alcohol substituents,polyhydric alcohol substituents, and combinations thereof.
 15. Thepolymeric composition of claim 11, wherein R^(2a), R^(2b), R^(2c),R^(2d), R^(3a), R^(3b), R^(4a), and R^(4b) have a formula of

wherein R⁵ is selected from the group consisting of —COOH, —CH₂CH₂OH,—(CH₂)₂—CH₂OH, —CH₂CH(OH)CH₂OH, —(CHOH)₂—CH₂OH, —C(O)NH₂, and—C(O)N(CH₃)₂.
 16. The polymeric composition of claim 11, wherein G andG′ are selected from the group consisting of vinyl, allyl, butadienyl,acryloyl, acryloyloxy, methacryloyl, methacryloyloxy, epoxy, itaconyl,maleimido, acrylamido, methacrylamido, fumaryl, styryl, and combinationsthereof.
 17. The polymeric composition of claim 11, wherein G and G′ arethe same or different and are selected from the group consisting ofvinyl, acryloyloxy, methacryloyloxy, and styryl.
 18. The polymericcomposition of claim 11, wherein each of D¹, D², D³, and D⁴ isindependently selected from the group consisting of saturated straightC₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and alkyloxy substituents.
 19. The polymeric compositionof claim 11, wherein Q is selected from the group consisting ofalkyleneoxy and poly(alkyleneoxy).
 20. The polymeric composition ofclaim 11, wherein Q is selected from the group consisting ofethyleneoxy, propyleneoxy, poly(ethyleneoxy), poly(propyleneoxy), andpoly(ethyleneoxy-propyleneoxy), and wherein a number of repeating unitsof each of said poly(ethyleneoxy), poly(propyleneoxy), andpoly(ethyleneoxy-propyleneoxy) groups is in a range from 2 to about 100.21. The polymeric composition of claim 11, further comprising units ofat least one additional monomer selected from the group consisting ofdifferent hydrophilic monomers and hydrophobic monomers.
 22. Thepolymeric composition of claim 21, wherein the additional monomer isselected from the group consisting of N,N′-dimethylacrylamide, glycerolmethacrylate, N-vinylpyrrolidone, and 2-hydroxyethyl methacrylate. 23.The polymeric composition of claim 21, wherein the additional monomer isselected from the group consisting of C₁-C₁₀ alkyl methacrylates, C₁-C₁₀alkyl acrylates, C₆-C₄₀ arylalkyl acrylates, C₆-C₄₀ arylalkylmethacrylates, and aromatic-based silicon-containing monomer.
 24. Thepolymeric composition of claim 21, wherein the additional monomer isselected from the group consisting of 2-phenylethyl acrylate,2-phenylethyl methacrylate, and combinations thereof.
 25. A method forproducing a polymeric material, the method comprising: (a) providing apolymerizable composition comprising a hydrophilic,arylsiloxy-containing macromonomer having a formula of

 wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same ordifferent and are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups, saturated straightC₁-C₁₀ hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups; D¹, D², D³, and D⁴are independently selected divalent linking groups; Q is a divalentgroup selected from the group consisting of divalent unsusbstitutedhydrocarbon groups, substituted hydrocarbon groups, alkyleneoxy groups,and poly(alkyleneoxy) groups; at least a plurality of E groups isindependently selected from the group consisting of unsubstituted andsubstituted pyrrolidone, hydroxyethyl group, ethoxyethanol group,ethoxymethoxy group, glyceryl group, amides, carboxylic acid, sulfonicacid, phosphonic acid, and alcohols; G and G′ are independently selectedfrom the group consisting of polymerizable functional groups; t and ware integers; 2≦t≦500; and 0≦w≦100; and (b) polymerizing thepolymerizable composition under a condition and for a time sufficient toproduce the polymeric material.
 26. The method of claim 25, wherein thepolymerizable composition further comprises an additional monomerselected from the group consisting of hydrophilic monomers, hydrophobicmonomers, and combinations thereof.
 27. An ophthalmic device comprisinga polymeric composition that comprises units of a hydrophilic,arylsiloxy-containing macromonomer having a formula of

wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same or differentand are selected from the group consisting of unsubstituted andsubstituted C₆-C₂₄ aromatic groups, saturated straight C₁-C₁₀hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups; D¹, D², D³, and D⁴are independently selected divalent linking groups; Q is a divalentgroup selected from the group consisting of divalent unsusbstitutedhydrocarbon groups, substituted hydrocarbon groups, alkyleneoxy groups,and poly(alkyleneoxy) groups; at least a plurality of E groups isindependently selected from the group consisting of unsubstituted andsubstituted pyrrolidone, hydroxyethyl group, ethoxyethanol group,ethoxymethoxy group, glyceryl group, amides, carboxylic acid, sulfonicacid, phosphonic acid, and alcohols; G and G′ are independently selectedfrom the group consisting of polymerizable functional groups; t and ware integers; 2≦t≦500; and 0≦w≦100.
 28. The ophthalmic device of claim27, wherein R^(2a), R^(2b), R^(2c), R^(2d), R^(3a), R^(3b), R^(4a), andR^(4b) are independently selected from the group consisting ofunsubstituted C₆-C₂₄ aromatic groups and C₆-C₂₄ aromatic groups havingat least a hydrophilic substituent.
 29. The ophthalmic device of claim28, wherein said at least a hydrophilic substituent is selected from thegroup consisting of carboxy, monohydric alcohol, polyhydric alcohol,alkoxy substituents, and combinations thereof.
 30. The ophthalmic deviceof claim 27 wherein R^(2a), R^(2b), R^(2c), R^(2d), R^(3a), R^(3b),R^(4a), and R^(4b) have a formula of

wherein R⁵ is selected from the group consisting of —COOH, —CH₂CH₂OH,—(CH₂)₂—CH₂OH, —CH₂CH(OH)CH₂OH, —(CHOH)₂—CH₂OH, —C(O)NH₂, and—C(O)N(CH₃)₂.
 31. The ophthalmic device of claim 27, wherein thepolymeric composition further comprises units of at least one additionalmonomer selected from the group consisting of hydrophilic monomers otherthan said hydrophilic, arylsiloxy-containing macromonomer; hydrophobicmonomers; and combinations thereof.
 32. The ophthalmic device of claim31, wherein the additional monomer is selected from the group consistingof N,N′-dimethylacrylamide, glycerol methacrylate, N-vinylpyrrolidone,and 2-hydroxyethyl methacrylate.
 33. The ophthalmic device of claim 31,wherein the additional monomer is selected from the group consisting ofC₁-C₁₀ alkyl methacrylates, C₁-C₁₀ alkyl acrylates, C₆-C₄₀ arylalkylacrylates, C₆-C₄₀ arylalkyl methacrylates, and aromatic-basedsilicon-containing monomers.
 34. The ophthalmic device of claim 31,wherein the additional monomer is selected from the group consisting of2-phenylethyl acrylate, 2-phenylethyl methacrylate, and combinationsthereof.
 35. The ophthalmic device of claim 27, wherein the polymericcomposition has a refractive index in a range from about 1.4 to about1.7.
 36. The ophthalmic device of claim 35, wherein the polymericcomposition has equilibrium absorbed water greater than about 4.5percent by weight.
 37. The ophthalmic device of claim 35, wherein theophthalmic device is selected from the group consisting of intraocularlenses, contact lenses, corneal rings, corneal inlays, andkeratoprostheses.
 38. A method for making an ophthalmic device, themethod comprising: (a) providing a polymerizable composition comprisinga hydrophilic, arylsiloxy-containing macromonomer having a formula of

 wherein R¹, R^(2a), R^(2b), R^(2c), and R^(2d) are the same ordifferent and are selected from the group consisting of unsubstitutedand substituted C₆-C₂₄ aromatic groups, saturated straight C₁-C₁₀hydrocarbons, unsaturated straight C₁-C₁₀ hydrocarbons, saturatedbranched C₃-C₁₀ hydrocarbons, unsaturated branched C₃-C₁₀ hydrocarbons,saturated cyclic C₃-C₁₀ hydrocarbons, unsaturated cyclic C₃-C₁₀hydrocarbons, and C₁-C₁₀ alkyloxy substituents; R^(3a), R^(3b), R^(4a),and R^(4b) are independently selected from the group consisting ofunsubstituted and substituted C₆-C₂₄ aromatic groups; D¹, D², D³, and D⁴are independently divalent linking groups; Q is a divalent groupselected from the group consisting of divalent unsusbstitutedhydrocarbon groups, substituted hydrocarbon groups, alkyleneoxy groups,and poly(alkyleneoxy) groups; at least a plurality of E groups isindependently selected from the group consisting of unsubstituted andsubstituted pyrrolidone, hydroxyethyl group, ethoxyethanol group,ethoxymethoxy group, glyceryl group, amides, carboxylic acid, sulfonicacid, phosphonic acid, and alcohols; G and G′ are independently selectedfrom the group consisting of polymerizable functional groups; t and ware integers; 2≦t≦500; and 0≦w≦100; and (b) curing the polymerizablecomposition under a condition and for a time sufficient to produce theophthalmic device.
 39. The method of claim 38, wherein the step ofcuring comprises solidifying the polymerizable composition in a moldcavity that forms a shape of the ophthalmic device.
 40. The method ofclaim 38, wherein the step of curing comprises solidifying thepolymerizable composition into a shaped article, and the method furthercomprises shaping the shaped article into the ophthalmic device.